Static headspace (HS) and capillary gas chromatography/infrared spectroscopy-mass spectrometry (GC/IR-MS) were used to collect, separate, identify and quantitate the oxidative and thermal decomposition products in heated triolein, trilinolein and esterified propoxylated glycerols (EPGs), EPG-08 oleate and EPG-08 linoleate. Approximately 4 L of each oil sample (triolein, trilinolein, EPG-08 oleate and EPG-08 linoleate) with and without added antioxidants were separately heated in a deep fat fryer at $\rm 190\sp\circ C$ for 12 h each day until each contained $\ge$20% polymeric material.The major volatile compounds in heated EPG-08 oleate and in heated triolein were heptane, octane, heptanal, octanal, (E)-2-decenal and (E)-2-undecenal. Heating EPG-08 oleate produced the volatile compounds butylcyclopentane, propylcyclohexane, 2-ethyl-4-methyl-1,3-dioxolane, 1-acetoxy-2-propanone, 2,2,4-trimethyl-1,3-dioxolane, 1,2-propanediol, 2-heptyl-4-methyl-1,3-dioxolane, and 4-methyl-2-octyl-1,3-dioxolane which are unique to EPG-08 oleate.The major volatile compounds in heated EPG-08 linoleate and in heated trilinolein were pentane, hexanal, (E)-2-heptenal, 2-pentylfuran, (E)-2-octenal, 1-octen-3-ol and (E,E)-2,4-decadienal. The identified volatile compounds from heated EPG-08 linoleate are those generally expected from the oxidative and thermal decomposition of linoleates, except 1-acetoxy-2-propanone and 1-hydroxy-2-propanone, which are associated with the decomposition of the polyol backbone.Supercritical fluid extraction (SFE) was used in conjunction with capillary GC/IR-MS to extract, separate and identify volatile compounds in heated EPG-08 oleate and soybean oil. Most of the volatile compounds identified in soybean oil are associated with the oxidative and thermal decomposition of linoleic acid. The volatile compounds identified in heated EPG-08 oleate were similar to those identified using HS-GC/IR-MS.